Issue 17, 2024

Cation and anion co-partial substitution induced centrosymmetric to noncentrosymmetric structural transformation to construct nonlinear-optical rare-earth oxythiogermanates

Abstract

Rational structural design and modification based on known compounds is an effective strategy to explore new nonlinear optical (NLO) materials. Here, three new rare-earth (RE) oxythiogermanates Eu18Ge9O5S31 (1), Ca3.32Eu14.68Ge9O5S31 (2) and Ba3Eu15Ge9O5S31 (3) were obtained by the novel cation and anion co-partial substitution strategy from the parent β-Eu2GeS4 (0), which induces centrosymmetric to noncentrosymmetric (NCS) structural transformation and NLO activities. They crystallize with a pseudo-zero dimensional structure in the chiral R3 space group, featuring almost linearly arranged isolated GeS4 and GeOS3 tetrahedra. Their optical band gaps were determined to be 2.18, 2.23 and 2.24 eV, respectively. 1 and 2 show balanced NLO properties with moderate second-harmonic generation (SHG) responses (0.5 and 0.6 × AGS) and high laser-induced damage thresholds (LIDTs) (3.3 × AGS). Moreover, theoretical calculations show that their NLO properties are determined by the synergistic effect of GeS4 and GeOS3 tetrahedra. This work enriches the chemistry of rarely studied RE oxychalcogenides and provides a fresh route for designing NCS structures targeting diverse applications.

Graphical abstract: Cation and anion co-partial substitution induced centrosymmetric to noncentrosymmetric structural transformation to construct nonlinear-optical rare-earth oxythiogermanates

Supplementary files

Article information

Article type
Research Article
Submitted
13 Mai 2024
Accepted
04 Jul 2024
First published
16 Jul 2024

Inorg. Chem. Front., 2024,11, 5458-5464

Cation and anion co-partial substitution induced centrosymmetric to noncentrosymmetric structural transformation to construct nonlinear-optical rare-earth oxythiogermanates

N. Zhang, M. Yang, W. Yao, W. Xu, W. Zhou, W. Liu and S. Guo, Inorg. Chem. Front., 2024, 11, 5458 DOI: 10.1039/D4QI01195C

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